EP0953594B1 - Weights for filling sportswear and novel cured polymer composite material which is dense, soft and flexible - Google Patents

Weights for filling sportswear and novel cured polymer composite material which is dense, soft and flexible Download PDF

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Publication number
EP0953594B1
EP0953594B1 EP99400905A EP99400905A EP0953594B1 EP 0953594 B1 EP0953594 B1 EP 0953594B1 EP 99400905 A EP99400905 A EP 99400905A EP 99400905 A EP99400905 A EP 99400905A EP 0953594 B1 EP0953594 B1 EP 0953594B1
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EP
European Patent Office
Prior art keywords
weight according
tungsten
composite material
garment
thermosetting
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EP99400905A
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German (de)
French (fr)
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EP0953594A1 (en
Inventor
Bernard Dubocage
Jacques Maucourt
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Safran Ceramics SA
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Societe Nationale des Poudres et Explosifs
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Classifications

    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B21/00—Exercising apparatus for developing or strengthening the muscles or joints of the body by working against a counterforce, with or without measuring devices
    • A63B21/06—User-manipulated weights
    • A63B21/0601—Special physical structures of used masses
    • A63B21/0607—Plastic masses, e.g. elastomers; Masses provided with plastic coverings
    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B21/00—Exercising apparatus for developing or strengthening the muscles or joints of the body by working against a counterforce, with or without measuring devices
    • A63B21/06—User-manipulated weights
    • A63B21/065—User-manipulated weights worn on user's body
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0887—Tungsten

Definitions

  • the present invention lies in the field of maintenance and rehabilitation of functions muscle.
  • Weight-bearing clothes for exercises body are well known to those skilled in the art.
  • US Patent 5,300,000 describes for example a glove loaded with weights made up of an elastomeric matrix thermoplastic, for example vinyl, loaded with lead shot.
  • Patent DE 3,532,512 describes a vest responsible for weights made of flexible plastic and flexible loaded with lead or iron powder.
  • weights are however not soft enough and flexible and prove to be quite poor in practice comfortable.
  • lead being a toxic metal, these weights can be dangerous for the user, especially during prolonged or repetitive use.
  • PCT patent WO 94/01183 describes a combination loaded with weight in the form of plates and made up of a lead core coated with plastic their providing flexibility.
  • the flexibility of the weights is however very limited, and increase the thickness of the duct coating quickly at too large weights.
  • the present invention solves this problem.
  • crosslinked composite material it is necessary understand that the polymeric organic matrix of the composite material is thermoset and constitutes a three-dimensional network.
  • clothing is meant any piece clothing suitable for covering in a manner adjusted to the minus a part of the human or animal body, as by example a jacket, a jumpsuit, pants, a shorts, a headband, a glove, a sleeve for the foot or the leg, a horse saddle.
  • “flexible” composite material it is necessary include a composite material having a modulus elasticity at 20 ° C between approximately 0.5 MPa and about 5 MPa and an elongation at break at 20 ° C between about 100% and about 400%, these mechanical characteristics being determined so usual using a traction machine.
  • thermoplastics such as materials EPDM elastomer composites (Ethylene, Propylene Diene Monomers) loaded with tungsten powder, with a modulus of elasticity at 20 ° C greater than 150 MPa and the elongation at break at 20 ° C is less than 30%.
  • EPDM elastomer composites Ethylene, Propylene Diene Monomers
  • the weights according to the invention which are not toxic and odorless, retain their elasticity and their flexibility, on the one hand at any temperature included between - 50 ° C and 80 ° C, and on the other hand when they are subject to rapid stresses (rapid efforts, violent and repeated). They also have a very high shock absorption in the event of efforts intense, falling or shocking, as well as weak sensitivity to humidity and perspiration.
  • body exercises weight-laden clothes are preferably intended for a sports training or a muscle rehabilitation but they may have other motivations such as the diagnosis of asymmetries functional.
  • the combinations for sports training are particularly preferred.
  • the weights according to the invention can for example be set up in fixed and precise housing of these clothes so as to respect the body diagram and the center of gravity of the individual.
  • Optimizing the effectiveness of these exercises tangible can be obtained, for each case particular, by a judicious choice of density, the hardness and elasticity of the material, of the mass, the size and thickness of the weight as well as the positioning of the weights on the different parts of the body.
  • the particle size of the powdery charge tungsten is preferably between 0.5 ⁇ m and 200 ⁇ m, better still between 0.5 ⁇ m and 100 ⁇ m.
  • the 1 ⁇ m-50 ⁇ m range is particularly preferred.
  • the charge tungsten powder is chosen from the group consisting of tungsten, mixtures of tungsten with another metal, tungsten alloys and tungsten compounds.
  • the charge tungsten powder is chosen from the group consisting of tungsten, iron-tungsten mixtures, ferrotungsten alloys, tungsten-nickel-iron alloys, tungsten carbide, oxides of tungsten and tungsten salts.
  • charges tungsten-based powder may include the alloys W / Fe / Cr, W / Fe / Si, W / Ni / Cu and W / Ni / Co.
  • the metallic charge represents between 15% and 60% by volume relative to the material composite, preferably between 30% and 60% by volume, and the density of the composite material is between 5 and 12.
  • weights according to the invention can be presented in any usual form of weight intended to load the clothing for body exercises, for example under in the form of plates or cylinders.
  • they are in the form of plates, the thickness of which is preferably included between 2 mm and 10 mm, and whose angles can be rounded.
  • the prepolymer liquid can also have reactive functions non-terminal, i.e. fixed along the chain constituting the prepolymer. These reactive functions not are preferably identical to the functions terminal.
  • this feature may not be an integer, which is usually the case, fact that a polymer very rarely consists of identical molecules, and that the functionality measured is only an average statistical functionality.
  • liquid polyethers examples include the polyoxypropylenes of formula as examples of liquid polyesters those of formula and as examples of liquid polyether-esters those of formula formulas in which x, y, z and n represent whole numbers.
  • the prepolymer liquid is a polybutadiene with mass Mn between 1000 and 5000.
  • This variant makes it possible, unexpected, composite materials of density included between 3 and 12, particularly soft, of Shore A hardness between 20 and 50, for example close to 35, and particularly flexible, with an elongation at the rupture at 20 ° C between 200% and 400%, for example close to 300%, and a modulus of elasticity at 20 ° C included between 0.5 MPa and 3 MPa, for example close to 1 MPa.
  • Weights for loading clothing for body exercises performed with such materials composites achieve a level of comfort use of clothing and body shaping weights without any common measure with the level hitherto achieved using the known weights of the state of the art.
  • the polybutadienic chain contains pending vinyl unsaturations and ethylenic unsaturations in the chain which can be in the cis position or in the trans position.
  • the polybutadiene comprises between 15% and 25% of vinyl unsaturations pending, by relative to the total number of unsaturations.
  • it also comprises between 50% and 60% of unsaturations in trans position and between 20% and 30% unsaturation in the cis position, by relative to the total number of unsaturations.
  • polybutadiene has hydroxyl functional endings and the crosslinking agent is a polyisocyanate, for example a diisocyanate such as toluylene diisocyanate (mixture 2,4 and 2,6) isomers, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, thus forming a network crosslinked polyurethane.
  • a polyisocyanate such as toluylene diisocyanate (mixture 2,4 and 2,6) isomers, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate
  • crosslinker is a diisocyanate
  • polybutadiene has functional carboxyl terminations and the crosslinking agent is a polyepoxide or a polyaziridine, thus forming a network crosslinked respectively ester-alcohol or ester-amine.
  • polyepoxides mention may be made of various epichlorohydrin and glycerol condensates, which are mixtures of di- and tri-epoxides comprising chlorinated residues, and as examples of polyaziridines mention may be made of tris 1- (2-methyl) -aziridinyl phosphine oxide (MAPO) and phenyl bis 1- (2-methyl) -aziridinyl phosphine oxide (phenyl MAPO).
  • MAPO 2-methyl-aziridinyl phosphine oxide
  • phenyl MAPO phenyl bis 1- (2-methyl) -aziridinyl phosphine oxide
  • crosslinker When the crosslinker is dysfunctional, uses a polybutadiene having a functionality in carboxyl function greater than 2.
  • the pasty composition thermosetting pourable also includes an agent plasticizer such as dioctyl azelate, sebacate dioctyl and dioctyl phthalate.
  • the pasty composition thermosetting pourable also includes an agent antioxidant like those well known in the industry rubber, in particular a phenol such as ditertiobutylparacresol.
  • the pasty composition thermosetting castable also includes a crosslinking catalyst to reduce the reaction time and / or temperature.
  • These catalysts are generally salts organic transition metals such as iron acetylacetonate, copper acetylacetonate, lead octoate, lead chromate and dilaurate of dibutyltin.
  • the pasty composition thermosetting pourable also includes a polyol chain extender, for example a diol like trimethylhexanediol or a triol like trimethylolpropane.
  • a polyol chain extender for example a diol like trimethylhexanediol or a triol like trimethylolpropane.
  • the pasty flowable composition thermosetting can for example be obtained by pre-mixing of the prepolymer in a mixer liquid with tungsten powder charge, in possibly presence of chain extender polyol, plasticizer and antioxidant at a temperature for example between 30 ° C and 80 ° C, and possibly at reduced pressure.
  • thermosetting pasty composition is then crosslinked by heating to a temperature between 60 ° C and 150 ° C, preferably between between 90 ° C and 120 ° C.
  • This premix is stirred and homogenized by heating at 60 ° C for 4 h under reduced pressure about 10 mm Hg. After cooling to room temperature and return to pressure atmospheric, the crosslinking catalyst is added stirring the mixture for about 2 min at 25 ° C.
  • crosslinking agent is then added and mixing at 40 ° C for about 10 min, under pressure reduced by approximately 10 mm Hg.
  • thermosetting pasty composition then obtained is then poured into a mold preheated to 110 ° C having the general shape of a parallelepiped rectangle 15 cm long, 13 cm wide and 5 mm thick, but whose angles are slightly rounded.
  • composition contained in the mold by heating for 6 h at 110 ° C.
  • the density of the composite material constituting this plate is 5.8 and its Shore A hardness, determined according to the standard ASTM D 2240 is 35.
  • the user was able to observe a level of comfort of use and conformation to the body of the weights never before achieved with traditional weights.

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biophysics (AREA)
  • Orthopedic Medicine & Surgery (AREA)
  • General Health & Medical Sciences (AREA)
  • Physical Education & Sports Medicine (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Professional, Industrial, Or Sporting Protective Garments (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Artificial Filaments (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Undergarments, Swaddling Clothes, Handkerchiefs Or Underwear Materials (AREA)

Abstract

Use of weights made from a crosslinked liquid copolymer with powdered tungsten-containing filler for attachment to garments used for physical fitness training. Weights for loading a garment for physical body fitness training consisting of a dense, soft and pliable composite of a crosslinked organic polymeric matrix and a powdered metallic filler dispersed in the matrix, made by heating a pasty castable thermosetting composition comprising (i) a liquid prepolymer with functional reactive terminal groups, having a molecular weight of 500-10000, selected from polybutadienes, polyesters, polyethers and polyether-esters; (ii) a crosslinking agent for the prepolymer; and (iii) a pulverulent tungsten-containing filler. Independent claims are also included for (1) the garment for physical body fitness training; and (2) the above composite.

Description

La présente invention se situe dans le domaine de l'entretien et de la rééducation des fonctions musculaires.The present invention lies in the field of maintenance and rehabilitation of functions muscle.

Elle concerne de nouveaux poids destinés à charger des vêtements pour exercices corporels, par exemple effectués dans un but d'entraínement sportif, ou bien encore de rééducation des fonctions musculaires.It concerns new weights intended to load clothing for body exercises, for example performed for the purpose of sports training, or further rehabilitation of muscle functions.

Elle concerne également de nouveaux matériaux composites polymériques réticulés, denses, mous et souples particulièrement adaptés pour réaliser de tels poids.It also relates to new materials crosslinked, dense, soft and flexible particularly suitable for making such weight.

Les vêtements chargés de poids pour exercices corporels sont bien connus de l'homme du métier.Weight-bearing clothes for exercises body are well known to those skilled in the art.

Le brevet US 5 300 000 décrit par exemple un gant chargé de poids constitués d'une matrice élastomérique thermoplastique, par exemple vinylique, chargée par de la grenaille de plomb.US Patent 5,300,000 describes for example a glove loaded with weights made up of an elastomeric matrix thermoplastic, for example vinyl, loaded with lead shot.

Le brevet DE 3 532 512 décrit un gilet chargé de poids constitués d'une matière plastique flexible et souple chargée par de la poudre de plomb ou de fer.Patent DE 3,532,512 describes a vest responsible for weights made of flexible plastic and flexible loaded with lead or iron powder.

Ces poids ne sont toutefois pas suffisamment mous et souples et s'avèrent en pratique assez peu confortables. De plus, le plomb étant un métal toxique, ces poids peuvent être dangereux pour l'utilisateur, notamment lors d'utilisations prolongées ou répétitives.These weights are however not soft enough and flexible and prove to be quite poor in practice comfortable. In addition, lead being a toxic metal, these weights can be dangerous for the user, especially during prolonged or repetitive use.

Le brevet PCT WO 94/01183 décrit une combinaison chargée de poids en forme de plaques et constitués d'un noyau en plomb revêtu par une matière plastique leur procurant une certaine flexibilité.PCT patent WO 94/01183 describes a combination loaded with weight in the form of plates and made up of a lead core coated with plastic their providing flexibility.

La souplesse des poids est toutefois très limitée, et augmenter l'épaisseur du revêtement conduit rapidement à des poids trop volumineux.The flexibility of the weights is however very limited, and increase the thickness of the duct coating quickly at too large weights.

Les vêtements connus chargés de poids pour exercices corporels sont donc particulièrement inconfortables et l'homme du métier est à la recherche de poids à la fois denses, très mous et très souples pouvant se conformer le mieux possible au corps lors des exercices, sans aucune gêne pour le sportif ou le patient, et constitués d'un matériau non toxique.Known weight-bearing clothes for body exercises are therefore particularly uncomfortable and the skilled person is looking dense, very soft and very flexible able to conform as best as possible to the body during exercises, without any discomfort for the sportsman or the patient, and made of a non-toxic material.

La présente invention permet de résoudre ce problème.The present invention solves this problem.

Elle a pour objet de nouveaux poids ayant les propriétés précitées recherchées et destinés à charger un vêtement pour exercices corporels.It relates to new weights having the aforementioned properties sought and intended to charge clothing for physical exercises.

Ces nouveaux poids destinés à charger un vêtement pour exercices corporels, qui sont constitués en un matériau composite dense et souple comprenant une matrice organique polymérique et une charge pulvérulente métallique dispersée dans la matrice polymérique, sont caractérisés en ce que le matériau composite est mou, réticulé et obtenu par chauffage d'une composition pâteuse coulable thermodurcissable comprenant :

  • un prépolymère liquide comportant des terminaisons fonctionnelles réactives, ayant une masse moléculaire moyenne en nombre (Mn) comprise entre 500 et 10000, choisi dans le groupe constitué par les polybutadiènes, les polyesters, les polyéthers et les polyéther-esters,
  • un agent réticulant de ce prépolymère,
  • une charge pulvérulente tungsténique.
These new weights intended to load a garment for physical exercises, which are made of a dense and flexible composite material comprising a polymer organic matrix and a metallic powdery charge dispersed in the polymer matrix, are characterized in that the composite material is soft, crosslinked and obtained by heating a flowable thermosetting pasty composition comprising:
  • a liquid prepolymer comprising reactive functional terminations, having a number average molecular mass (Mn) of between 500 and 10,000, chosen from the group consisting of polybutadienes, polyesters, polyethers and polyether-esters,
  • a crosslinking agent for this prepolymer,
  • a tungsten powder charge.

L'état physique, pâteux de la composition et liquide du prépolymère, doit être apprécié dans les conditions normales de température et de pression.The physical, pasty state of the composition and liquid of the prepolymer, must be appreciated in normal temperature and pressure conditions.

Par matériau composite « réticulé », il faut comprendre que la matrice organique polymérique du matériau composite est thermodurcie et constitue un réseau tridimensionnel.By “crosslinked” composite material, it is necessary understand that the polymeric organic matrix of the composite material is thermoset and constitutes a three-dimensional network.

Par « vêtement », il faut comprendre toute pièce d'habillement apte à recouvrir de manière ajustée au moins une partie du corps humain ou animal, comme par exemple une veste, une combinaison, un pantalon, un short, un serre-tête, un gant, un manchon pour le pied ou la jambe, une selle pour cheval.By "clothing" is meant any piece clothing suitable for covering in a manner adjusted to the minus a part of the human or animal body, as by example a jacket, a jumpsuit, pants, a shorts, a headband, a glove, a sleeve for the foot or the leg, a horse saddle.

Par matériau composite « dense », il faut comprendre un matériau composite dont la densité est comprise entre environ 3 et environ 12.By "dense" composite material, it is necessary understand a composite material whose density is between approximately 3 and approximately 12.

Par matériau composite « mou », il faut comprendre un matériau composite présentant une dureté Shore A, déterminée selon la méthode bien connue de l'homme du métier, comprise entre environ 20 et environ 50.By "soft" composite material, we must understand a composite material having a Shore A hardness, determined according to the method well known to man of the trade, between approximately 20 and approximately 50.

Par matériau composite « souple », il faut comprendre un matériau composite présentant un module d'élasticité à 20°C compris entre environ 0,5 MPa et environ 5 MPa ainsi qu'un allongement à la rupture à 20°C compris entre environ 100% et environ 400%, ces caractéristiques mécaniques étant déterminées de façon usuelle à l'aide d'une machine de traction.By “flexible” composite material, it is necessary include a composite material having a modulus elasticity at 20 ° C between approximately 0.5 MPa and about 5 MPa and an elongation at break at 20 ° C between about 100% and about 400%, these mechanical characteristics being determined so usual using a traction machine.

Il est particulièrement surprenant que de tels matériaux composites, denses donc fortement chargés, et réticulés, puissent être aussi mous et souples, plus mous et plus souples que la plupart des matériaux denses thermoplastiques connus, comme par exemple les matériaux composites à base d'élastomère EPDM (Ethylène, Propylène Diène Monomères) chargés par du tungstène en poudre, dont le module d'élasticité à 20°C est supérieur à 150 MPa et l'allongement à la rupture à 20°C est inférieur à 30%.It is particularly surprising that such composite materials, dense therefore highly charged, and cross-linked, can be as soft and flexible, more soft and softer than most dense materials known thermoplastics, such as materials EPDM elastomer composites (Ethylene, Propylene Diene Monomers) loaded with tungsten powder, with a modulus of elasticity at 20 ° C greater than 150 MPa and the elongation at break at 20 ° C is less than 30%.

Ces matériaux composites polymériques réticulés, denses, mous et souples particulièrement adaptés pour réaliser des poids destinés à charger des vêtements pour exercices corporels, sont, à notre connaissance, nouveaux.These crosslinked polymer composite materials, dense, soft and flexible particularly suitable for carry weights to load clothes for body exercises, are, to our knowledge, new.

Lors des exercices, de tels poids se conforment parfaitement au corps sans aucune gêne pour l'utilisateur et sans aucun mouvement de ces poids par rapport au corps, ce qui évite tout risque de blessure pendant des exercices violents et procure un confort jamais atteint jusqu'alors.During exercises, such weights conform perfectly to the body without any discomfort for the user and without any movement of these weights by body, which avoids any risk of injury during violent exercises and provides comfort never reached before.

De plus, les poids selon l'invention, qui sont non toxiques et sans odeur, conservent leur élasticité et leur souplesse, d'une part à toute température comprise entre - 50°C et 80°C, et d'autre part lorsqu'ils sont soumis à des sollicitations rapides (efforts rapides, violents et répétés). Ils possèdent par ailleurs un pouvoir amortissant au choc très élevé en cas d'efforts intenses, de chutes ou de chocs, ainsi qu'une faible sensibilité à l'humidité et à la transpiration.In addition, the weights according to the invention, which are not toxic and odorless, retain their elasticity and their flexibility, on the one hand at any temperature included between - 50 ° C and 80 ° C, and on the other hand when they are subject to rapid stresses (rapid efforts, violent and repeated). They also have a very high shock absorption in the event of efforts intense, falling or shocking, as well as weak sensitivity to humidity and perspiration.

Selon l'invention, les exercices corporels réalisés à l'aide des vêtements chargés de poids sont de préférence destinés à un entraínement sportif ou à une rééducation musculaire, mais ils peuvent avoir d'autres motivations telle que le diagnostic d'asymétries fonctionnelles.According to the invention, body exercises weight-laden clothes are preferably intended for a sports training or a muscle rehabilitation but they may have other motivations such as the diagnosis of asymmetries functional.

Les combinaisons pour l'entraínement sportif sont particulièrement préférées.The combinations for sports training are particularly preferred.

Les poids selon l'invention peuvent par exemple être mis en place dans des logements fixes et-précis de ces vêtements de façon à respecter le schéma corporel et le centre de gravité de l'individu.The weights according to the invention can for example be set up in fixed and precise housing of these clothes so as to respect the body diagram and the center of gravity of the individual.

L'optimisation de l'efficacité de ces exercices corporels peut être obtenue, pour chaque cas particulier, par un choix judicieux de la densité , de la dureté et de l'élasticité du matériau, de la masse, de la taille et de l'épaisseur du poids ainsi que du positionnement des poids sur les différentes parties du corps.Optimizing the effectiveness of these exercises tangible can be obtained, for each case particular, by a judicious choice of density, the hardness and elasticity of the material, of the mass, the size and thickness of the weight as well as the positioning of the weights on the different parts of the body.

La granulométrie de la charge pulvérulente tungsténique est de préférence comprise entre 0,5 µm et 200 µm, mieux encore entre 0,5 µm et 100 µm.The particle size of the powdery charge tungsten is preferably between 0.5 μm and 200 µm, better still between 0.5 µm and 100 µm.

Le domaine 1µm-50µm est particulièrement préféré. The 1µm-50µm range is particularly preferred.

Selon une variante préférée, la charge pulvérulente tungsténique est choisie dans le groupe constitué par le tungstène, les mélanges de tungstène avec un autre métal, les alliages du tungstène et les composés du tungstène.According to a preferred variant, the charge tungsten powder is chosen from the group consisting of tungsten, mixtures of tungsten with another metal, tungsten alloys and tungsten compounds.

De façon particulièrement préférée, la charge pulvérulente tungsténique est choisie dans le groupe constitué par le tungstène, les mélanges fer-tungstène, les alliages ferrotungstènes, les alliages tungstène-nickel-fer, le carbure de tungstène, les oxydes de tungstène et les sels de tungstène.Particularly preferably, the charge tungsten powder is chosen from the group consisting of tungsten, iron-tungsten mixtures, ferrotungsten alloys, tungsten-nickel-iron alloys, tungsten carbide, oxides of tungsten and tungsten salts.

Comme autres exemples non limitatifs de charges pulvérulentes à base de tungstène pouvant convenir, on peut citer les alliages W/Fe/Cr, W/Fe/Si, W/Ni/Cu et W/Ni/Co.As other nonlimiting examples of charges tungsten-based powder may be suitable, may include the alloys W / Fe / Cr, W / Fe / Si, W / Ni / Cu and W / Ni / Co.

De façon préférée, la charge métallique représente entre 15% et 60% en volumes par rapport au matériau composite, de préférence entre 30% et 60% en volumes, et la densité du matériau composite est comprise entre 5 et 12.Preferably, the metallic charge represents between 15% and 60% by volume relative to the material composite, preferably between 30% and 60% by volume, and the density of the composite material is between 5 and 12.

Les poids selon l'invention peuvent se présenter sous toute forme usuelle de poids destinés à charger les vêtements pour exercices corporels, par exemple sous forme de plaques ou de cylindres.The weights according to the invention can be presented in any usual form of weight intended to load the clothing for body exercises, for example under in the form of plates or cylinders.

De façon préférée, ils se présentent sous forme de plaques, dont l'épaisseur est de préférence comprise entre 2 mm et 10 mm, et dont les angles peuvent être arrondis.Preferably, they are in the form of plates, the thickness of which is preferably included between 2 mm and 10 mm, and whose angles can be rounded.

Par ailleurs, selon l'invention, le prépolymère liquide peut comporter également des fonctions réactives non terminales, c'est à dire fixées le long de la chaíne constituant le prépolymère. Ces fonctions réactives non terminales sont de préférence identiques aux fonctions terminales.Furthermore, according to the invention, the prepolymer liquid can also have reactive functions non-terminal, i.e. fixed along the chain constituting the prepolymer. These reactive functions not are preferably identical to the functions terminal.

On obtient, dans ce cas, une fonctionnalité en fonctions réactives supérieure à 2, par exemple comprise entre 2,0 et 2,5.One obtains, in this case, a functionality in reactive functions greater than 2, for example included between 2.0 and 2.5.

Bien entendu, cette fonctionnalité peut ne pas être un nombre entier, ce qui est en général le cas, du fait qu'un polymère n'est que très rarement constitué de molécules identiques, et que la fonctionnalité mesurée n'est qu'une fonctionnalité moyenne statistique.Of course, this feature may not be an integer, which is usually the case, fact that a polymer very rarely consists of identical molecules, and that the functionality measured is only an average statistical functionality.

Selon l'invention, comme exemples de polyéthers liquides, on peut citer les polyoxypropylènes de formule

Figure 00060001
comme exemples de polyesters liquides ceux de formule
Figure 00060002
et comme exemples de polyéther-esters liquides ceux de formule
Figure 00060003
formules dans lesquelles x, y, z et n représentent des nombres entiers.According to the invention, as examples of liquid polyethers, mention may be made of the polyoxypropylenes of formula
Figure 00060001
as examples of liquid polyesters those of formula
Figure 00060002
and as examples of liquid polyether-esters those of formula
Figure 00060003
formulas in which x, y, z and n represent whole numbers.

De façon particulièrement préférée le prépolymère liquide est un polybutadiène de masse Mn comprise entre 1000 et 5000.Particularly preferably the prepolymer liquid is a polybutadiene with mass Mn between 1000 and 5000.

Cette variante permet d'obtenir, de façon inattendue, des matériaux composites de densité comprise entre 3 et 12, particulièrement mous, de dureté Shore A comprise entre 20 et 50, par exemple voisine de 35, et particulièrement souples, avec un allongement à la rupture à 20°C compris entre 200% et 400%, par exemple voisin de 300%, et un module d'élasticité à 20°C compris entre 0,5 MPa et 3 MPa, par exemple voisin de 1 MPa.This variant makes it possible, unexpected, composite materials of density included between 3 and 12, particularly soft, of Shore A hardness between 20 and 50, for example close to 35, and particularly flexible, with an elongation at the rupture at 20 ° C between 200% and 400%, for example close to 300%, and a modulus of elasticity at 20 ° C included between 0.5 MPa and 3 MPa, for example close to 1 MPa.

Les poids destinés à charger des vêtements pour exercices corporels réalisés avec de tels matériaux composites permettent d'atteindre un niveau de confort d'utilisation des vêtements et de conformation au corps des poids sans aucune commune mesure avec le niveau jusqu'alors atteint en utilisant les poids connus de l'état de la technique.Weights for loading clothing for body exercises performed with such materials composites achieve a level of comfort use of clothing and body shaping weights without any common measure with the level hitherto achieved using the known weights of the state of the art.

De façon générale, la chaíne polybutadiénique comporte des insaturations vinyliques pendantes et des insaturations éthyléniques dans la chaíne pouvant être en position cis ou en position trans.In general, the polybutadienic chain contains pending vinyl unsaturations and ethylenic unsaturations in the chain which can be in the cis position or in the trans position.

De façon préférée, le polybutadiène comporte entre 15% et 25% d'insaturations vinyliques pendantes, par rapport au nombre total des insaturations.Preferably, the polybutadiene comprises between 15% and 25% of vinyl unsaturations pending, by relative to the total number of unsaturations.

De façon également préférée, il comporte également entre 50% et 60% d'insaturations en position trans et entre 20% et 30% d'insaturations en position cis, par rapport au nombre total des insaturations.Also preferably, it also comprises between 50% and 60% of unsaturations in trans position and between 20% and 30% unsaturation in the cis position, by relative to the total number of unsaturations.

Selon une variante préférée, le polybutadiène comporte des terminaisons fonctionnelles hydroxyles et l'agent réticulant est un polyisocyanate, par exemple un diisocyanate comme le diisocyanate de toluylène (mélange des isomères 2,4 et 2,6), le 4,4'-diphénylméthane diisocyanate, l'hexaméthylène diisocyanate, l'isophorone diisocyanate, permettant de former ainsi un réseau réticulé polyuréthanne.According to a preferred variant, polybutadiene has hydroxyl functional endings and the crosslinking agent is a polyisocyanate, for example a diisocyanate such as toluylene diisocyanate (mixture 2,4 and 2,6) isomers, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, thus forming a network crosslinked polyurethane.

Lorsque le réticulant est un diisocyanate, on utilise un polybutadiène de fonctionnalité en hydroxyles supérieure à 2, par exemple de l'ordre de 2,2, et/ou on ajoute dans la composition thermodurcissable un polyol extenseur de chaíne ayant une fonctionnalité en hydroxyles supérieure à 2, comme le triméthylolpropane.When the crosslinker is a diisocyanate, uses a polybutadiene with hydroxyl functionality greater than 2, for example of the order of 2.2, and / or adds a polyol to the thermosetting composition chain extender with functionality in hydroxyls greater than 2, such as trimethylolpropane.

Selon une autre variante, le polybutadiène comporte des terminaisons fonctionnelles carboxyles et l'agent réticulant est un polyépoxyde ou une polyaziridine, permettant de former ainsi un réseau réticulé respectivement ester-alcool ou ester-amine.According to another variant, polybutadiene has functional carboxyl terminations and the crosslinking agent is a polyepoxide or a polyaziridine, thus forming a network crosslinked respectively ester-alcohol or ester-amine.

Comme exemples de polyépoxydes, on peut citer les divers condensats d'épichlorhydrine et de glycérol, qui sont des mélanges de di- et de tri-époxydes comportant des restes chlorés, et comme exemples de polyaziridines on peut citer le tris 1-(2-méthyl)-aziridinyl phosphine oxyde (MAPO) et le phényl bis 1-(2-méthyl)-aziridinyl phosphine oxyde (phényl MAPO).As examples of polyepoxides, mention may be made of various epichlorohydrin and glycerol condensates, which are mixtures of di- and tri-epoxides comprising chlorinated residues, and as examples of polyaziridines mention may be made of tris 1- (2-methyl) -aziridinyl phosphine oxide (MAPO) and phenyl bis 1- (2-methyl) -aziridinyl phosphine oxide (phenyl MAPO).

Lorsque le réticulant est difonctionnel, on utilise un polybutadiène ayant une fonctionnalité en fonction carboxyles supérieure à 2.When the crosslinker is dysfunctional, uses a polybutadiene having a functionality in carboxyl function greater than 2.

Selon une autre variante, la composition pâteuse coulable thermodurcissable comprend également un agent plastifiant comme l'azélate de dioctyle, le sébaçate de dioctyle et le phtalate de dioctyle.According to another variant, the pasty composition thermosetting pourable also includes an agent plasticizer such as dioctyl azelate, sebacate dioctyl and dioctyl phthalate.

Selon une autre variante, la composition pâteuse coulable thermodurcissable comprend également un agent antioxydant comme ceux bien connus de l'industrie du caoutchouc, notamment un phénol comme le ditertiobutylparacrésol.According to another variant, the pasty composition thermosetting pourable also includes an agent antioxidant like those well known in the industry rubber, in particular a phenol such as ditertiobutylparacresol.

Selon une autre variante, la composition pâteuse coulable thermodurcissable comprend également un catalyseur de réticulation permettant de réduire le temps et/ou la température de réaction.According to another variant, the pasty composition thermosetting castable also includes a crosslinking catalyst to reduce the reaction time and / or temperature.

Ces catalyseurs sont en général des sels organiques de métaux de transition, comme l'acétylacétonate de fer, l'acétylacétonate de cuivre, l'octoate de plomb, le chromate de plomb et le dilaurate de dibutyl-étain.These catalysts are generally salts organic transition metals such as iron acetylacetonate, copper acetylacetonate, lead octoate, lead chromate and dilaurate of dibutyltin.

Selon une autre variante, la composition pâteuse coulable thermodurcissable comprend également un polyol extenseur de chaíne, par exemple un diol comme le triméthylhexanediol ou un triol comme le triméthylolpropane.According to another variant, the pasty composition thermosetting pourable also includes a polyol chain extender, for example a diol like trimethylhexanediol or a triol like trimethylolpropane.

Selon l'invention, la composition pâteuse coulable thermodurcissable peut par exemple être obtenue par mélange préalable, dans un malaxeur, du prépolymère liquide avec la charge pulvérulente tungsténique, en présence éventuellement du polyol extenseur de chaíne, du plastifiant et de l'antioxydant, à une température par exemple comprise entre 30°C et 80°C, et éventuellement à pression réduite.According to the invention, the pasty flowable composition thermosetting can for example be obtained by pre-mixing of the prepolymer in a mixer liquid with tungsten powder charge, in possibly presence of chain extender polyol, plasticizer and antioxidant at a temperature for example between 30 ° C and 80 ° C, and possibly at reduced pressure.

On ajoute ensuite le catalyseur éventuel, puis ensuite l'agent réticulant du prépolymère.Then adding the optional catalyst, then then the crosslinking agent of the prepolymer.

Après mélange, à une température par exemple comprise entre 30°C et 50°C, et de préférence à pression réduite, jusqu'à l'obtention d'une pâte homogène, celle-ci est coulée dans des moules à la forme choisie pour les poids, par exemples des plaques d'épaisseur comprise entre 2 mm et 10 mm.After mixing, at a temperature for example between 30 ° C and 50 ° C, and preferably at pressure reduced, until a homogeneous paste is obtained, this is poured into molds of the shape chosen for the weights, for example plates of thickness included between 2 mm and 10 mm.

La composition pâteuse thermodurcissable est ensuite réticulée par chauffage à une température comprise entre 60°C et 150°C, de préférence comprise entre 90°C et 120°C.The thermosetting pasty composition is then crosslinked by heating to a temperature between 60 ° C and 150 ° C, preferably between between 90 ° C and 120 ° C.

Après refroidissement du moule, on obtient, par démoulage, des matériaux composites polymériques réticulés, denses, mous et souples utilisables directement comme poids destinés à charger un vêtement pour exercices corporels.After the mold has cooled, mold release, polymer composite materials crosslinked, dense, soft and flexible usable directly as weights intended to load a garment for body exercises.

La présente invention a également pour objet les nouveaux matériaux composites polymériques réticulés, denses, mous et souples précités, à savoir de nouveaux matériaux composites denses et souples comprenant une matrice organique polymérique et une charge pulvérulente métallique dispersée dans la matrice polymérique, caractérisés en ce que ces matériaux composites sont mous, réticulés, et obtenus par chauffage d'une composition pâteuse coulable thermodurcissable comprenant :

  • un prépolymère liquide comportant des terminaisons fonctionnelles réactives, ayant une masse Mn comprise entre 500 et 10 000, choisi dans le groupe constitué par les polybutadiènes, les polyéthers, les polyesters et les polyéther-esters, de préférence un polybutadiène ayant une masse Mn comprise entre 1000 et 5000,
  • un agent réticulant de ce prépolymère,
  • une charge pulvérulente tungsténique.
The present invention also relates to the above-mentioned new dense, soft and flexible crosslinked polymeric composite materials, namely new dense and flexible composite materials comprising a polymeric organic matrix and a metallic powdery filler dispersed in the polymeric matrix, characterized in that these composite materials are soft, crosslinked, and obtained by heating a pasty thermosetting pasty composition comprising:
  • a liquid prepolymer comprising reactive functional terminations, having a mass Mn of between 500 and 10,000, chosen from the group consisting of polybutadienes, polyethers, polyesters and polyether-esters, preferably a polybutadiene having a mass Mn of between 1000 and 5000,
  • a crosslinking agent for this prepolymer,
  • a tungsten powder charge.

L'exemple non limitatif suivant illustre l'invention et les avantages qu'elle procure.The following nonlimiting example illustrates the invention and the advantages it provides.

On réalise, par mélange des divers constituants dans un réacteur en verre de 1 litre, une composition pâteuse coulable thermodurcissable ayant la composition massique suivante :

  • polybutadiène à terminaisons hydroxyles, de masse Mn environ 2300, de fonctionnalité en hydroxyles proche de 2,2, comportant 20% d'insaturations vinyliques pendantes, 25% d'insaturations dans la chaíne en position cis et 55% d'insaturations dans la chaíne en position trans   : 100,0 g
  • alcool court extenseur de chaíne : triméthylhexanediol (TMHD)   : 13,2 g
  • plastifiant : azélate de dioctyle
    (DOZ)   : 71,6 g
  • antioxydant : ditertiobutylparacrésol (DBPC)   : 1,0 g
  • charge pulvérulente métallique : alliage W/Ni/Fe 92/5/3 respectivement en poids de granulométrie 5-10 µm et de densité 19   : 1600 g
  • catalyseur de réticulation
    dibutyldilaurate d'étain (DBTL)   : 1,8 g
  • agent réticulant : mélange des
    isomères 2,4 et 2,6 du toluylène
    diisocyanate (Dis-T ou TDI ou Desmodur T)   : 21,2 g
A thermosetting flowable pasty composition having the following mass composition is produced by mixing the various constituents in a 1 liter glass reactor.
  • polybutadiene with hydroxyl endings, of mass Mn about 2300, of hydroxyl functionality close to 2.2, comprising 20% of pendant vinyl unsaturations, 25% of unsaturations in the chain in the cis position and 55% of unsaturations in the chain trans position: 100.0 g
  • short chain extender alcohol: trimethylhexanediol (TMHD): 13.2 g
  • plasticizer: dioctyl azelate
    (DOZ): 71.6 g
  • antioxidant: ditertiobutylparacresol (DBPC): 1.0 g
  • metallic powdery charge: alloy W / Ni / Fe 92/5/3 respectively by weight of particle size 5-10 µm and density 19: 1600 g
  • crosslinking catalyst
    tin dibutyldilaurate (DBTL): 1.8 g
  • crosslinking agent: mixture of
    2,4 and 2,6 isomers of toluylene
    diisocyanate (Dis-T or TDI or Desmodur T): 21.2 g

Pour réaliser ce mélange, on effectue tout d'abord un prémélange de l'alcool court, du plastifiant et de l'antioxydant, puis on ajoute le polybutadiène à terminaisons hydroxyles et la charge pulvérulente métallique.To achieve this mixture, first of all a premix of short alcohol, plasticizer and the antioxidant and then we add polybutadiene to hydroxyl endings and powdery charge metallic.

On agite et homogénéise ce prémélange par chauffage à 60°C durant 4 h sous pression réduite d'environ 10 mm Hg. Après refroidissement à la température ambiante et retour à la pression atmosphérique, on ajoute le catalyseur de réticulation en agitant le mélange 2 min environ à 25°C.This premix is stirred and homogenized by heating at 60 ° C for 4 h under reduced pressure about 10 mm Hg. After cooling to room temperature and return to pressure atmospheric, the crosslinking catalyst is added stirring the mixture for about 2 min at 25 ° C.

On ajoute ensuite l'agent réticulant, puis on mélange à 40°C durant 10 min environ, sous pression réduite d'environ 10 mm Hg.The crosslinking agent is then added and mixing at 40 ° C for about 10 min, under pressure reduced by approximately 10 mm Hg.

La composition pâteuse thermodurcissable alors obtenue est ensuite coulée dans un moule préchauffé à 110°C ayant la forme générale d'un parallélépipède rectangle de longueur 15 cm, de largeur 13 cm et d'épaisseur 5 mm, mais dont les angles sont légèrement arrondis.The thermosetting pasty composition then obtained is then poured into a mold preheated to 110 ° C having the general shape of a parallelepiped rectangle 15 cm long, 13 cm wide and 5 mm thick, but whose angles are slightly rounded.

On réticule ensuite la composition contenue dans le moule par chauffage durant 6 h à 110°C.The composition contained in the mold by heating for 6 h at 110 ° C.

Après refroidissement du moule à la température ambiante, on démoule une plaque ayant les dimensions précitées du moule, directement utilisable, après saupoudrage éventuel de talc, comme poids destiné à charger un vêtement pour exercices corporels.After cooling the mold to temperature ambient, we unmold a plate having the dimensions aforementioned mold, directly usable, after possible dusting of talc, as a weight intended for load clothing for body exercises.

La densité du matériau composite constituant cette plaque, déterminée selon la méthode par immersion, est de 5,8 et sa dureté Shore A, déterminée selon la norme ASTM D 2240 est de 35.The density of the composite material constituting this plate, determined by the immersion method, is 5.8 and its Shore A hardness, determined according to the standard ASTM D 2240 is 35.

On a par ailleurs déterminé (6 mesures), à l'aide d'une machine de traction classique, à partir d'éprouvettes monodimensionnelles normalisées, à 20°C sous une humidité relative de 40%, avec une vitesse de traction de 50 mm/min, les propriétés mécaniques du matériau composite constituant cette plaque

  • Module d'élasticité (E)   : 1,09 ± 0,07 MPa
  • Allongement à la rupture (er)   : 280 ± 20%
  • Contrainte maximale (Sm)   : 1,8 ± 0,1 MPa
  • Allongement à la contrainte
    maximale (em)   : 270 ± 20%.
    • We also determined (6 measurements), using a conventional tensile machine, from standard one-dimensional test pieces, at 20 ° C under a relative humidity of 40%, with a tensile speed of 50 mm. / min, the mechanical properties of the composite material constituting this plate
  • Modulus of elasticity (E): 1.09 ± 0.07 MPa
  • Elongation at break (e r ): 280 ± 20%
  • Maximum stress (Sm): 1.8 ± 0.1 MPa
  • Stress elongation
    maximum (e m ): 270 ± 20%.

    • Après réalisation de plusieurs plaques identiques à celles précitées, celles-ci ont été utilisées comme poids pour charger une combinaison pour exercices corporels telle que celle décrite dans le brevet PCT précité WO 94/01183.After making several identical plates to those mentioned above, these have been used as weight to load an exercise suit such as that described in the PCT patent cited above WO 94/01183.

    L'utilisateur a pu constater un niveau de confort d'utilisation et de conformation au corps des poids jamais atteint jusqu'alors avec les poids traditionnels.The user was able to observe a level of comfort of use and conformation to the body of the weights never before achieved with traditional weights.

    Claims (22)

    1. A weight intended to load a garment for body exercises, said weight being made of a dense and supple composite material comprising a polymeric organic matrix and a metallic pulverulent charge dispersed within said polymeric matrix, characterised in that the composite material is soft and reticulate and is obtained by heating a thermosetting pourable pasty composition comprising:
      a liquid prepolymer containing reactive functional terminations and having a mass between 500 and 10,000, chosen from the group constituted by the polybutadienes, the polyesters, the polyethers and the polyether esters,
      a crosslinking agent for said prepolymer,
      a tungstic pulverulent charge.
    2. Weight according to Claim 1, characterised in that the reticulate composite material exhibits a Shore-A hardness between 20 and 50, a modulus of elasticity at 20°C between 0.5 MPa and 5 MPa and an elongation at rupture at 20°C between 100% and 400%.
    3. Weight according to Claim 1, characterised in that the garment for body exercises is a garment intended for sports training or for muscle rehabilitation.
    4. Weight according to Claim 1, characterised in that it takes the form of a panel.
    5. Weight according to Claim 4, characterised in that the panel has a thickness between 2 mm and 10 mm.
    6. Weight according to Claim 1, characterised in that the relative density of the composite material is between 3 and 12 and in that the tungstic pulverulent charge represents between 15 % and 60 % by volume relative to the composite material.
    7. Weight according to Claim 1, characterised in that the tungstic pulverulent charge is chosen from the group constituted by tungsten, mixtures of tungsten with another metal, alloys of tungsten and compounds of tungsten.
    8. Weight according to Claim 7, characterised in that the tungstic pulverulent charge is chosen from the group constituted by tungsten, iron/tungsten mixtures, ferrotungsten alloys, tungsten/nickel/iron alloys, tungsten carbides, tungsten oxides and tungsten salts.
    9. Weight according to Claim 1, characterised in that the liquid prepolymer also contains non-terminal reactive functional groups.
    10. Weight according to Claim 1, characterised in that the liquid prepolymer is a polybutadiene with a mass between 1000 and 5000.
    11. Weight according to Claim 10, characterised in that the composite material exhibits a Shore-A hardness between 20 and 50, a modulus of elasticity at 20°C between 0.5 MPa and 3 MPa and an elongation at rupture at 20°C between 200 % and 400 %.
    12. Weight according to Claim 10, characterised in that the reactive functional terminations of the polybutadiene are. hydroxyl groups and in that the crosslinking agent is a polyisocyanate.
    13. Weight according to Claim 12, characterised in that the thermosetting pourable pasty composition also comprises a chain-extender polyol.
    14. Weight according to Claim 10, characterised in that the reactive functional terminations of the polybutadiene are carboxyl groups and in that the crosslinking agent is a polyepoxide or a polyaziridine.
    15. Weight according to Claim 1, characterised in that the thermosetting pourable pasty composition also comprises a plasticiser.
    16. Weight according to Claim 1, characterised in that the thermosetting pourable pasty composition also comprises an anti-oxidant.
    17. Weight according to Claim 1, characterised in that the thermosetting pourable pasty composition also comprises a crosslinkage catalyst.
    18. Weight according to Claim 1, characterised in that the heating-temperature is between 60°C and 150°C.
    19. A garment for body exercises, characterised in that it is loaded by at least one weight according to one of the preceding claims.
    20. Garment according to Claim 19, characterised in that said garment is a suit for sports training.
    21. A dense and supple composite material comprising a polymeric organic matrix and a metallic pulverulent charge dispersed within said polymeric matrix, characterised in that said composite material is soft and reticulate and is obtained by heating a thermosetting pourable pasty composition comprising:
      a liquid prepolymer containing reactive functional terminations and having a mass between 500 and 10,000, chosen from the group constituted by the polybutadienes, the polyesters, the polyethers and the polyether esters,
      a crosslinking agent for said prepolymer,
      a tungstic pulverulent charge.
    22. Composite material according to Claim 21, characterised in that the liquid prepolymer is a polybutadiene with a mass between 1000 and 5000.
    EP99400905A 1998-04-28 1999-04-14 Weights for filling sportswear and novel cured polymer composite material which is dense, soft and flexible Expired - Lifetime EP0953594B1 (en)

    Applications Claiming Priority (2)

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    FR9805288A FR2777789B1 (en) 1998-04-28 1998-04-28 WEIGHTS FOR LOADING CLOTHING FOR BODY EXERCISES AND NEW CROSSLINKED, DENSES, SOFT AND FLEXIBLE POLYMER COMPOSITE MATERIALS
    FR9805288 1998-04-28

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    JP4663072B2 (en) * 2000-07-31 2011-03-30 Ｓｒｉスポーツ株式会社 Tennis racket with a dynamic damper
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    CA3087749A1 (en) 2017-01-06 2018-07-12 Lawrence T. Petrakis Breathable heavyweight garments for physical conditioning
    US20180271194A1 (en) * 2017-03-23 2018-09-27 Laika, LLC Weighted lining for garment, costume or other object
    CL2017001875A1 (en) * 2017-07-21 2017-12-11 Sanz Sebastian Martinoli Material with weight for sportswear
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